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Conjugated Thermolysis of Metal-Containing Monomers: Toward Core–Shell Nanostructured Advanced Materials

  • Gulzhian I. Dzhardimalieva
  • Igor E. UflyandEmail author
Article
  • 116 Downloads

Abstract

A detailed analysis of recent advances in the use of metal-containing monomers as precursors for the preparation of core–shell nanostructured advanced materials by the method of conjugated thermolysis was carried out. This method consists in the simultaneous course of the processes of thermal polymerization of monomers and the formation of metal-containing nanoparticles during thermal transformation. The general scheme of conjugated thermolysis includes three successive stages: dehydration (desolvation), polymerization and thermolysis of the resulting metallopolymers. Particular attention was paid to the composition of solid-phase products of conjugated thermolysis. Kinetic schemes and reactions of thermal transformation of metal-containing monomers were analyzed. The use of the obtained nanocomposites as magnetic materials, sensors, catalysts and tribological materials was generalized. Problems and prospects of using conjugated thermolysis for the production of advanced nanomaterials were outlined.

Keywords

Conjugated thermolysis Core–shell structure Metal-containing monomer Nanomaterial Thermal polymerization 

Abbreviations

AAm

Acrylamide

Acr

Acrylate ion

ADC

Acetylenedicarboxylate ion

APS

Average particle size

Bpy

2,2′-Bipyridine

COF

Coefficient of friction

DTA

Differential thermal analysis

DTG

Differential thermogravimetry

ETXRD

Elevated temperature X-ray diffraction

FC

Field cooling mode

Fum

Fumarate ion

HRTEM

High-resolution transmission electron microscopy

LPG

Liquefied petroleum gas

Mal

Maleate ion

MCM

Metal-containing monomer

NP

Nanoparticle

phen

1,10-Phenantroline

Py

Pyridine

SEM

Scanning electron microscopy

SGA

Self-generated atmosphere

TA

Thermal analysis

TEM

Transmission electron microscopy

TG

Thermogravimetry

TGA

Thermogravimetric analysis

XRD

X-ray diffraction

ZFC

Zero-field cooling mode

1 Introduction

In recent years, metallopolymer nanostructured materials have become the subject of intensive research from the point of view of the fundamental aspects of the structure and functional properties [1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11]. The interest in such materials is due to the unique combination of the attractive physicochemical properties of nanoscale metals, their oxides, carbides or chalcogenides with film-forming, mechanical and other characteristics of polymers [12, 13, 14, 15, 16]. The properties of nanomaterials due to size and shape include a quantum-size effect, a surface and interface effect, as well as a macroscopic quantum tunnel effect [17, 18, 19]. In particular, the quantization of electronic states becomes obvious, which leads to very sensitive size-dependent effects, such as optical, electrical, and magnetic properties [20, 21, 22, 23]. In addition, a high surface-to-volume ratio contributes to the formation of a large number of potential active sites on their surface. It is now generally accepted that the properties of nanomaterials, their technological performance and areas of use are largely determined by the structure, morphology, shape, size and other characteristics of nanoparticles (NPs) [24, 25]. The inclusion of metal nanoparticles in a polymer matrix provides numerous advantages [26, 27, 28]. Firstly, it helps to ensure increased stability of the NPs, which have a high tendency to agglomerate. Secondly, nanostructured materials exhibit significantly improved properties compared to pure polymers or their traditional composites. The undoubted advantages of nanostructured materials over other types of nanomaterials are due to the possibility of their easy modification for the target production of materials of different composition, morphology, size and surface properties [29].

The unique properties of nanostructured materials allowed them to be used for recording and storing information [30], in medicine [31, 32, 33, 34, 35, 36, 37], and biology [38, 39, 40], for applications based on surface-enhanced Raman scattering (SERS) [41], and irradiation [42], for enhanced oil recovery [43], as intelligent environmental [44] and optical materials [45, 46], for the detection of pollutants [47], smart windows [48], etc.

Various approaches have been developed to obtain nanostructured materials, including sol–gel syntheses, intercalation processes, chemical precipitation and reduction reactions in polymer matrices, etc. [1, 2]. The combined use of various methods allows to obtain hybrid structures and new materials for a wide range of applications, for example, as smart membranes, catalysts, sensors, drug delivery systems, etc. [49, 50]. The development and improvement of metallopolymer nanostructured materials can not only significantly improve the quality of functional materials, but also lead to the creation of new generations of materials that meet the technological requirements of modern production [51, 52].

Core–shell nanostructured materials are of interest due to their promising properties and a wide range of applications in biology, catalysis, materials chemistry and sensors [53, 54, 55]. Traditional methods for producing such materials are usually laborious and include a number of successive stages, for example, the preparation of metal-polymer complexes, the reduction of metal ions to the zero-valent state, the separation of unreacted components [1, 2, 56, 57, 58]. In addition, these methods lead to the formation of polydisperse systems, and the resulting NPs are very reactive and are characterized by a high propensity for aggregation.

In this regard, an important task is the search for one-step methods for obtaining core–shell nanostructured materials. Such methods should include simultaneous synthesis of the polymer matrix, nucleation and growth of NPs, which is important for solving the problem of stabilization of NPs by polymers and their spatial organization. Of particular interest is the approach based on the conjugated thermolysis of metal-containing monomers (MCMs), which includes their thermal polymerization and the thermolysis of the resulting metallopolymers [59, 60, 61]. MCMs are metal complexes containing multiple bonds capable of entering into (co)polymerization reactions [62, 63, 64, 65].

Our group began studying the conjugated thermolysis of MCMs 30 years ago under the guidance of Professor A.D. Pomogailo, who was the Head of the Laboratory of metallopolymers at the Institute of Problems of Chemical Physics of the Russian Academy of Sciences [66]. Over the years, many of our research papers were published in the Journal of Inorganic and Organometallic Polymers [62, 67, 68, 69, 70, 71, 72], and its special issue (6, 2016) was dedicated to Professor A.D. Pomogailo (guest editor G.I. Dzhardimalieva). This review focuses on the main advances in the field of conjugated thermolysis of MCMs and the production of core–shell nanostructured advanced materials. This direction of research has been developing very intensively in recent years, because it may be the best embodiment of the idea of stabilizing NPs in situ. The rapid growth of research in this area makes this review timely.

2 General Scheme of Conjugated Thermolysis

Studying the conjugated thermolysis of MCMs in the thermal analysis (TA) mode makes it possible to obtain only qualitative information on their thermal transformations. A complete picture of the influence of various factors on the kinetics of conjugated thermolysis can be obtained by isothermal studies in self-generated atmosphere (SGA). These studies showed a general pattern of the conjugated thermolysis of MCMs, consisting of three main stages [1, 59, 61]: dehydration (desolvation) of the initial MCMs, thermal polymerization of dehydrated MCMs and thermolysis of the resulting metallopolymers. The last stage is accompanied by intense gas evolution and leads to the formation of metal-containing NPs and polymer matrix. In many cases, these stages overlap.

2.1 Dehydration

Dehydration of monomeric crystalline hydrates occurs at low temperatures of thermolysis (Ttherm). For example, according to the studies of thermogravimetry (TG), differential thermal analysis (DTA) and differential thermogravimetry (DTG), dehydration of acrylates (Acr) and maleates (Mal) of metals occurs at 353–487 (FeAcr3), 413–453 (CoAcr2), 373–473 (NiAcr2), 393–433 (CoMal) and 373-433 K (FeMal) [61]. A special case is CoAcr2, which is characterized by a two-stage evaporation process under isothermal conditions at 303–433 K [73]. Evaporation at 303–348 K is associated with evaporation of crystalline water, \({\text{P}}_{{{\text{H}}_{ 2} {\text{O}}}} \left( {{\text{T}}_{\text{therm}} } \right)\, = \, 1. 7\, \times \, 10^{ 7} { \exp }\left[ { - \, 9 200/{\text{RT}}} \right]\,{\text{kPa}}\), and the heat of evaporation ΔHst(H2O) = 38.5 kJ mol−1 is close to heat of evaporation of pure H2O, ΔHevap(H2O) = 43.9 kJ mol−1. At the same time, evaporation at Ttherm > 348 K is described by the dependence \({\text{P}}_{{{\text{H}}_{ 2} {\text{O}}}} \left( {{\text{T}}_{\text{therm}} } \right)\, = \, 2. 7\, \times \, 10^{ 4} { \exp }\left[ { - \, 4 800/{\text{RT}}} \right]\,{\text{kPa}}\) and is directly related to the dehydration of CoAcr2, ΔHevap(H2O) = 20.1 kJ mol−1. A two-stage dehydration process has also been established for CoMal with endothermic effects at 400 and 433 K [74]. For acidic Mn(II), Fe(II), Co(II) and Ni(II) maleates, the removal of coordinated water also proceeds in two stages, which correlates with the M–O (H2O) distance in the coordination octahedron containing two water molecules in two different positions [75].

Terbium fumarate heptahydrate Tb2(Fum)3·7H2O loses all seven (four coordinated and three lattice) water molecules at 311–423 K [76]. Non-isothermal kinetics was used to estimate the activation energy of the dehydration stage of the thermolysis of this compound using the Coats–Redfern integral method [77]:
$$\ln \left[ {\frac{g\left( \alpha \right)}{{T^{2} }}} \right] = \ln \left( {\frac{AR}{E\beta }\left( {1 - \frac{2RT}{E}} \right)} \right) - \frac{E}{RT}$$
(1)
where α is the fraction of reagent used, g(α) is the conversion function depending on the reaction mechanism, R is the gas constant, E is the activation energy, T is the absolute temperature, β is the linear heating rate, and A is the frequency factor.
The plot of ln \(\left[ {\frac{g\left( \alpha \right)}{{T^{2} }}} \right]\) versus 1/T gives a straight line for the correct model. The two-dimensional nucleation model D (A2) with an activation energy of 51.064 kJ mol−1 showed the maximum correlation coefficient (Fig. 1).
Fig. 1

Plot of ln \(\left[ {\frac{g\left( \alpha \right)}{{T^{2} }}} \right]\) versus 1/T for the dehydration stage of the terbium fumarate complex: 1—diffusion models of 1D diffusion (D1), 2—Avarami-Erofe’ev nucleation model (A3), 3—Avarami-Erofe’ev nucleation model (A3), 4—3D diffusion—the Jander Eq. (D3), 5—geometrical contraction model contracting area (R2), 6—geometrical contraction model contracting volume (R3), 7—2D diffusion (D2), 8—Ginstling–Brounshtein (D4). Red line is linear fit [77]

[Zn(H2O)4(Fum)]·H2O decomposes when heated in two stages, and the initial endothermic dehydration proceeds at 318–353 K [78]. The TG curves of the compounds [Co(Fum)(H2O)4]·H2O, [Co(Fum)(Py)2(H2O)2] and [Co(Fum)(4-CNPy)2(H2O)2], where Py is pyridine, show that the first complex undergoes dehydration at 352–518 K with the release of five water molecules [79]. The second complex loses two coordinated water molecules together with the Py molecule at 359–478 K. The first stage of the third compound thermolysis is associated with the loss of two water molecules together with the 4-CNPy molecule. At the same time, the first stage of thermolysis of the analogous nickel complex, catena[μ-fumaratobis(4-cyanopyridine)diaquanickel(II)], the first stage of thermolysis involves the release of two 4-CNPy molecules at 418–578 K [80]. The most striking aspect of a thermogram is the lack of stages associated with weight loss due to dehydration. Apparently, before the temperature reaches 578 K, water molecules participate in the formation of fumaric acid, and the resulting hydroxyl groups remain attached to the metal ion as ligands. When heated, the dehydration of fumarates of trivalent lanthanides proceeds in one and two successive stages [81, 82].

Manganese coordination polymers {Mn(Fum)(5,5′-dimethyl-bpy)(H2O)2}n and {[Mn2(Fum)2(4,4′-dimethyl-bpy)2]·H2O}n (bpy is 2,2′-bipyridine) are characterized by three main stages of thermolysis [83]. In both complexes, the first stage of thermolysis can be attributed to the loss of water; however, the first complex loses two coordinated water ligands, and the second complex is characterized by the loss of only one molecule of crystallization water.

During dehydration in vacuum, the crystalline hydrates CoADC·2H2O and ZnADC·2H2O, where ADC is an acetylenedicarboxylate ion, are stable only up to a certain minimum content of coordination water [84].

2.2 Polymerization

A subsequent increase in temperature leads to thermal polymerization of dehydrated (desolvated) MCMs. As an example, we note the typical temperature ranges of such polymerization of metal acrylates and maleates: ~ 543 K (CoAcr2), ~ 563 (NiAcr2), ~ 510 (CuAcr2), ~ 518 (FeAcr3), 488–518 (CoMal), ~ 518 K (FeMal) [61]. It is important that in this temperature range there is a slight evolution of gas and a small weight loss of the sample (≪ 10 wt%).

An increase in temperature contributes to an increase in the level of thermal vibrations of the lattice of dehydrated (desolvated) MCMs, which leads to the break of the weakest M–O bonds and the formation of monoradical CH2=CHCOO or diradical OOCCH=CHCOO of ligands in the case of acrylates and maleates, respectively [76, 85]. As a result of the subsequent interaction of these radicals with other molecules of MCMs, the corresponding acids and the radical R with the hydrogen-depleted acrylate (maleate) group are formed. This radical is the initiator of the formation of linearly structured metallopolymers. In the case of metal dicarboxylates, a comb-shaped linear metallopolymer is formed, which has the usual structure in the first stage and a three-dimensional network in the subsequent stage. As an example, Scheme 1 shows the processes of initiation and polymerization of complexes of cobalt acrylate with bpy and phen, where phen is 1,10-phenanthroline [86].
Scheme 1

Scheme of second stage of thermolysis of MCMs (L = bpy or phen)

The thermal transformations of ZnADC·2H2O and CoADC·2H2O in vacuum lead to the formation of the so-called “boiling layer”, which is characterized by a significant entrainment of solid particles from the reactor (Fig. 2) [84]. It should be noted that the vigorous release of gaseous products during the thermolysis of crystalline hydrates is not associated with a certain characteristic temperature and is observed even at low heating rates. For example, for ZnADC·2H2O, this temperature is 403, 415, and 421 K at heating rates of 0.8, 1.6, and 2.4° min−1, respectively.
Fig. 2

Temperature dependences of relative weight loss for ZnADC.2H2O (1, 2, and 4) and CoADC·2H2O (3) in vacuum. The heating rate is 0.8 (1), 1.6 (2) and 2.4 deg min−1 (3, 4) [84]

However, most of the results of studies of thermal transformations of MCMs are qualitative.

It should be noted that the thermal polymerization of some MCMs proceeds in the frontal (autowave) mode. In the 1990s, the phenomenon of frontal polymerization of metal-containing monomers was first discovered in our laboratory [87], but for a long time it was limited to the example of acrylamide (AAm) complexes of transition metal nitrates [88, 89, 90, 91, 92, 93, 94, 95, 96]. Recently, we found that copper(II) cinnamate complexes with polypyridine ligands (bpy, phen and 4′-phenyl-2.2′,6′,2″-terpyridine) are also subjected to frontal polymerization [97]. A schematic diagram of frontal polymerization is shown in Fig. 3 [98].
Fig. 3

 Schematic for frontal polymerization reaction technique [98]

2.3 Thermolysis

At the final stage of thermolysis, thermopolymerized MCMs undergo decarboxylation with intensive evolution of gases (Scheme 2) [61]. This process takes place in the following temperature ranges: 363–513 (CuAcr2), 623–663 (CoAcr2), 573–633 (NiAcr2), 473–643 (FeAcr3), 613–633 (FeCoAcr), 613–633 (Fe2CoAcr), 603–643 (Fe2NiAcr), 613–643 (CoMal), 573–643 K (FeMal).
Scheme 2

Scheme of decarboxylation process, where R′=CH2=CH–CH=CH is hydrogen-depleted decarboxylated diacrylate fragment; MOx is the metal (x = 0) or its oxide (x > 0)

The gas evolution rate monotonously decreases with an increase in the degree of conversion (η), and the kinetics of the evolution of the gas η(τ) in the general case (up to η ≤ 0.95) is satisfactorily approximated by the equation for two parallel reactions [81]:
$$\eta (\tau ) = \eta_{{ 1 {\text{f}}}} [ 1- { \exp }({-}{\text{ k}}_{ 1} \tau )] + \left( { 1- \eta_{{ 1 {\text{f}}}} } \right)\left[ { 1- { \exp }( - {\text{ k}}_{ 2} \tau )} \right]$$
(2)
where τ = t – t0 (t0 is the heating time), \(\eta_{{ 1 {\text{f}}}} \, = \,\eta ({\text{t}})\left| {_{{{\text{k}}_{ 2} {\text{t}} \to 0,{\text{ k}}_{ 1} {\text{t}} \to \infty ,}} {\text{k}}_{ 1} ,{\text{ k}}_{ 2} } \right.\) are the effective rate constants.
Parameters k1, k2, η1f, Δα∑, f depend on the thermolysis temperature. The initial gas evolution rate Wτ=0 = W0 is
$${\text{W}}_{0} = \eta_{{ 1 {\text{f}}}} {\text{k}}_{ 1} + ( 1- \eta_{{ 1 {\text{f}}}} ){\text{k}}_{ 2}$$
(3)
The kinetics of the gas evolution during thermolysis of NiAcr2, FeCoAcr, Fe2CoAcr, Fe2NiAcr, and FeMal is described by Eqs. (2) and (3).
When k2 ≈ 0, η1f → 1
$$\eta (\tau ) \approx 1- { \exp }( - \,{\text{k}}_{ 1} \tau ),{\text{ W}}_{0} \approx {\text{k}}_{ 1}$$
(4)

Equation (4) describes the kinetics of the gas evolution during the thermolysis of CoAcr2 and CoMal.

In the case when τ ≪ 1/k2, k1 ≫ k2,
$$\eta (\tau ) \approx \eta_{{ 1 {\text{f}}}} [ 1- { \exp }({-}{\text{ k}}_{ 1} \tau )] + ( 1- \eta_{{ 1 {\text{f}}}} ){\text{k}}_{ 2} \tau ,{\text{ W}}_{0} \approx \eta_{{ 1 {\text{f}}}} {\text{k}}_{ 1}$$
(5)

Dependence η(τ) during thermolysis of CuAcr2 is satisfactorily described by Eq. (5).

Kinetic parameters of gas evolution during thermolysis of MCMs are presented in Table 1 [99, 100].
Table 1

Kinetic parameters of thermolysis of metal-containing monomers

Compound

η1f, Δα∑, f = Aexp[− Ea,eff/(RTtherm)]

k

keff = k0,effexp [− Ea,eff/(RTtherm)]

W0 = k0,effexp[− Ea,eff/(RTtherm)]

η1f, Δα∑, f

A

Ea,eff, kJ mol−1

 

k0,eff, s−1

Ea,eff, kJ mol−1

k0,eff, s−1

Ea,eff, kJ mol−1

CuAcr2

η1f

Δα∑, f

1.8 × 104

3.6

48.1

12.5

k1

k2

9.5 × 1011

9.2 × 1011

154.7

163.0

9.5 × 1011

202.7

CoAcr2

η1f,

Δα∑, f

1.0

1.55

0

0

k1

k2

3.0 × 1014

0

238.3

0

3.0 × 1014

238.3

FeAcr3 (473–573 K)

(573–643 K)

η1f

Δα∑, f

η1f,

Δα∑, f

1.0

1.6 × 102

1.0

1.7 × 102

0

25.5

0

26.3

k1

k2

k1

k2

4.2 × 1021

0

1.3 × 106

0

246.5

0

127.5

0

4.2 × 1021

1.3 × 106

246.5

127.5

NiAcr2

η1f

Δα∑, f < 593 K

Δα∑, f > 633 K

2.6

1.4 × 1011

1.2

4.6

125.4

10.5

k1

k2

1.7 × 1017

7.5 × 108

242.4

156.7

4.4 × 1017

247.0

FeCoAcr

η1f = 0.45 (663 K)–0.65 (613 K)

k1

2.3 × 1012

207.0

1.3 × 1012

207.0

Δα∑, f

5.25 × 102

31.3

k2

6.0 × 106

138.0

  

Fe2CoAcr

η1f = 0.35 (663 K)–0.50 (613 K)

k1

2.6 × 1012

205.0

1.1 × 1012

205.0

Δα∑, f

1.5 × 102

25.1

k2

6.6 × 105

125.5

  

Fe2NiAcr

η1f

4.4 × 107

75.0

k1

6.1 × 106

129.5

2.7 × 1014

205.0

Δα∑, f

6.5 × 102

25.5

k2

0.6 × 102

79.4

  

CoMal

η1f

1.0

0

k1

1.1 × 106

125.4

1.1 × 106

125.4

Δα∑, f

1.3 × 102

23.4

k2

0

0

  

FeMal

η1f

0.59 × 102

23.4

k1

3.3 × 107

133.8

1.9 × 109

157.2

Δα∑,f = 4.78 (573 K)–7.40 (643 K)

k2

1.0 × 107

110.8

  

Thermolysis of FeAcr3 is characterized by two regions of gas evolution at 473–573 and 603–643 K [101]. The gas evolution rate in these regions is well described by Eqs. (2, 3), but with different values of k and Δα∑, f (see Table 1). Probably, the difference in the kinetic parameters in these regions during thermolysis of FeAcr3, as well as FeCoAcr, Fe2CoAcr, Fe2NiAcr is due to the presence of two parallel processes of gas evolution.

According to the values of W0, the reactivity of acrylate and maleate MCMs in the process of thermolysis can be represented as follows: Cu ≥ Fe > Co > Ni. Interestingly, the effective activation energies of the initial gas evolution rate under SGA conditions for CuAcr2 (202.7 kJ mol−1) and NiAcr2 (246.6 kJ mol−1), shown in Table 1, are close to the calculated values for thermolysis in the TA regime: 211.1 and 244.1 kJ mol−1, respectively [102]. However, for CoAcr2, this value in the SGA regime (238.3 kJ mol−1) is higher than the corresponding value in TA conditions (206.1 kJ mol−1). It should be note the difference in the rate constants of gas evolution during thermolysis of CoAcr2 and CoMal, as well as the proximity of the activation parameters of FeMal and FeAcr3, FeCoAcr, Fe2CoAcr, Fe2NiAcr in the same temperature range.

The end products of the thermolysis of the resulting metallopolymers are metal (or its oxide) and CO2.
$${\text{R}}^{\text{I}} {- }\left[ {{-}\left( {{\text{M}}_{{ 1 / {\text{n}}}} {\text{OOC}}} \right){\text{CH}} {-} {\text{CH}}\left( {{\text{COOM}}_{{ 1 / {\text{n}}}} } \right) {-} } \right]_{s} {-} {\text{R}}^{\text{I}} \to {\text{ CH}} {\equiv} {\text{C}} {-} \left[ { - {\text{CH}} {-} {\text{CH}}{ -} } \right]_{\text{s}} {-} {\text{C}} {\equiv} {\text{CH}} + 2\left( {{\text{s }} + \, 2} \right){\text{CO}}_{2} + {\text{ M}}$$
(6)

Oxygen-free polymers can be additionally thermopolymerized to form network structures with conjugated multiple bonds.

3 The Composition and Structure of the Solid-Phase Products of Conjugated Thermolysis

The products of thermolysis of MCMs are stable over time; in particular, during long-term storage, there is no change in the chemical composition, size and shape of the NPs. According to electron microscopy, they have similar morphological structures in which electron-dense particles are present in a less electron-dense matrix [61]. Thus, the thermolysis of MCMs leads to the formation of metal-polymer nanostructured materials, which contain metal, oxide, or carbide NPs evenly distributed in stabilizing polymer matrices.

The average particle diameter (dav) is shown in Table 2.
Table 2

The average size of the spherical particles in polymer matrix

Sample

CoAcr2

FeAcr3

FeCoAcr

Fe2CoAcr

Fe2NiAcr

CoMal

dav, nm

7

7–9

5–6

5–6

6-8

3–4

The obtained NPs are individual or form aggregates of 3-10 particles. In addition, they have a close to spherical shape and a narrow size distribution (Fig. 4) [103].
Fig. 4

TEM (transmission electron microscopy) microstructure (left) and electron diffraction (right) of the metallic particles distributed in a polymer matrix obtained by the thermolysis of CoAcr2 at 643 K [103]

The metal cores of the thermolysis products of acrylate MCMs contain significant amounts of shells from metal oxides or carbides. For example, in the thermolysis product of CoAcr2, the CoO content in the core reaches 85 wt%, and the thermolysis product of NiAcr2 contains Ni0 ≈ 43, NiO ≈ 35 and Ni3C ≈ 22 wt%, respectively [104].

Among the factors that have a significant effect on the rate of solid-phase chemical reactions, it should be noted morphological characteristics of the reagents (dispersion, specific surface area and particle topography). In particular, the initial MCMs are optically transparent crystal-like porous particles that have a relatively large specific surface area (Table 3) [99]. As a result of thermolysis, the average particle size (APS) decreases, while Ssp increases by a factor of 2–3, and then decreases again due to sintering of the particles [71, 99]. In the early stages of thermolysis, the particles lose their transparency, and their surface becomes sugar-like, which may indicate a significant contribution to the bulk homogeneous reaction. Thus, the thermolysis of MCMs is a heterogeneous-homogeneous process [102, 105, 106, 107, 108].
Table 3

The dispersion of the initial MCMs and their thermolysis products

MCM

S0,sp (m2 g−1)

Sf,sp (m2 g−1)

APS (μm)

CuAcr2

14.7

48.0 (463 K)–53.8 (473 K)–43.8 (503 K)

5–50

CoAcr2

20.2

24.1 (623 K)–42.1 (663 K)

100–150

FeAcr3

15.0

15.0

1–5

NiAcr2

16.0

55.0–60.5

60–100

FeCoAcr

9.0

13.6

5–10

Fe2CoAcr

8.1

11.3

10–15

Fe2NiAcr

8.5

13.5

100–200

CoMal

30.0

30.0

5–70

FeMal

24.0

26.0

30–50

The core of the thermolysis products of unsaturated cobalt hydrogen carboxylates in an argon stream consists of two structural elements: Co3O4 NPs (cubic symmetry) with small impurities of CoO (tetragonal symmetry) and metallic cobalt (hexagonal symmetry) [109]. The products of thermolysis of CuMal are aggregates with sizes ranging from 100 nm to 8 μm (Fig. 5) [110]. After 7 days of storage in air, they show the Cu2O phase in addition to the metallic phase, and longer storage leads to almost complete oxidation of the copper.
Fig. 5

Photograph of CuMal thermolysis product [110]

The composition and monophasic homogeneity of transition metal maleates are decisive factors in the thermolysis process, which is accompanied by graphitization of the matrix and NPs [75, 111, 112]. In addition, the conditions of thermolysis (temperature and atmosphere), the ligand environment, and the nature of the metal in the initial MCMs determine the paths of thermolysis. In particular, metal-polymer core–shell nanocomposites containing metal NPs uniformly distributed in a stabilizing nitrogen-containing polymer matrix were obtained by thermolysis of MCMs based on Ni(II) cinnamate and chelating N-heterocycles (bpy and phen) at 573 K [113]. At the same time, the thermolysis products of the same compounds at 723 K are pure nickel oxide NPs (Scheme 3). It should be emphasized that the nature of the chelating ligand affects the structure and size of the product obtained.
Scheme 3

The effect of thermolysis temperature on the composition of thermolysis products

Various thermolysis products were also obtained in the case of nickel carboxylates (Table 4): NiO and β-Ni (nickel itaconate, acetylenedicarboxylate and allyl malonate), NiO, β-Ni and impurities of α-Ni (nickel maleate and cis,cis-muconate), NiO, β-Ni and α-Ni (nickel glutaconate) [108].
Table 4

XRD results for thermolysis products of nickel(II) carboxylates

MCM

Phase

Symmetry system

Space group

Unit cell parameters, Å

Content, wt %

Nickel maleate

NiO

Cubic

Fm3m

a = 4.184

33.4 ± 0.1

β-Ni

Cubic

Fm3m

a = 3.519

57.3 ± 0.1

α-Ni

Hexagonal

P63/mmc

9.3 ± 0.1

Nickel itaconate

NiO

Cubic

Fm3m

a = 4.175

73.3 ± 0.1

Cubic

Fm3m

a = 3.523

26.7 ± 0.1

α-Ni

Hexagonal

Nickel acetylenedicarboxylate

NiO

Cubic

Fm3m

a = 4.176

73.7 ± 0.1

β-Ni

Cubic

Fm3m

a = 3.525

26.3 ± 0.1

α-Ni

Hexagonal

Nickel allylmalonate

NiO

Cubic

Fm3m

a = 4.178

67.8 ± 0.0

β-Ni

Cubic

Fm3m

a = 3.522

32.2 ± 0.0

α-Ni

Hexagonal

Nickel glutaconate

NiO

Cubic

Fm3m

a = 4.178

21.6 ± 0.1

β-Ni

Cubic

Fm3m

a = 3.521

56.8 ± 0.1

α-Ni

Hexagonal

P63/mmc

a = 2.485

c = 4.093

21.5 ± 0.1

Nickel cis,cis-muconate

NiO

Cubic

Fm3m

a = 4.197

30.0 ± 0.2

β-Ni

Cubic

Fm3m

a = 3.517

66.8 ± 0.2

α-Ni

Hexagonal

P63/mmc

2.9 ± 0.1

It is of interest to obtain bimetallic nanostructured materials by thermolysis of solid solutions of transition metals, whose parameters (conductivity, catalytic activity and magnetic properties) differ from monometallic NPs. As an example, we note the following solid solutions: acidic Co(II) maleate–acidic Ni(II) maleate, acidic Fe(II) maleate–acidic Co(II) maleate and acidic Fe(II) maleate–acidic Ni(II) maleate [114]. It is important that when heated, the obtained bimetallic nanocomposites undergo a second-order phase transition from an ordered paramagnetic state to an unordered ferromagnetic state.

An example of the dependence of the composition of products on the atmosphere of thermolysis is cadmium itaconate monohydrate [115]. In particular, CdO was obtained in air; cadmium oxide, traces of metallic cadmium and cadmium hydroxide prevailed in the atmosphere of N2, and metallic cadmium dominated in the atmosphere of H2.

The products of thermolysis of metal acetylenedicarboxylates are polymeric matrices with a uniform distribution of metal-containing NPs [116]. It turned out that NPs of iron (< 10 nm) and cobalt (10–20 nm) are spherical, and NPs of zinc (~ 20 nm) have the form of plates (Fig. 6).
Fig. 6

SEM (ac) and TEM images (df) of the thermolysis products of CoADC (a, d), FeADC (b, e), and ZnADC (c, f), where SEM is scanning electron microscopy [116]

An increase in the thermolysis temperature of the coordination polymer Zn(L)(ADC), where L is 4,4′-bipyridine, leads to the formation of more uniform rods with a longer length (Fig. 7) [117].
Fig. 7

SEM images of ZnO nanorods obtained by thermolysis of Zn(L)(ADC) at 673 (a), 773 (b) and 873 K (c) [117]

Spherical silver NPs embedded in a carbon matrix were synthesized by thermolysis of AgADC at 573 K in an autoclave or in a xylene suspension at boiling point [118]. Interestingly, in the latter case, an insignificant proportion of quasicrystalline silver is formed. Graphite layers covering silver NPs are clearly visible in high-resolution transmission electron microscopy (HRTEM) images (Fig. 8).
Fig. 8

HRTEM images of the thermolysis products of AgADC. In the last image a single silver NP and its typical interlayer spacing is shown in magnification [118]

Metal fumarates were shown to can be used for the synthesis of metal carbide NPs [119, 120]. An elevated temperature X-ray diffraction (ETXRD) made it possible to determine the crystalline phases obtained by thermolysis of the corresponding MCMs (Fig. 9) [121]. In particular, iron fumarate formed Fe3C at 773 and 823 K, but decomposed to BCC-Fe at higher temperatures. The product obtained at 823 K contains 60–70% Fe3C with a grain size of 107 nm.
Fig. 9

ETXRD scans and TGA-IR contour plots for the thermolysis of iron fumarate [121]

The conditions of the thermolysis of iron and nickel complexes with AAm determine the size and shape of the formed NPs (Fig. 10) [122]. In particular, an increase in the thermolysis temperature results in an increase in the particle size, and this effect is more pronounced for iron NPs. It is important that the high thermolysis temperature (873 K) leads not only to the aggregation of metal particles, but also to the formation of a shell of Fe3C metal carbide surrounding the iron core. The size of metal NPs varies from 5 to 20 nm, depending on the nature of the metal and the conditions of thermolysis.
Fig. 10

TEM micrographs of Fe NPs obtained at 873 K for 120 min (a), 773 K for 120 min (b) and 673 K for 60 min (c), as well as Ni NPs obtained at 873 K for 60 min (d) and 673 K for 60 min (e) [122]

The core–shell structure of the obtained nanostructured materials is schematically shown in Fig. 11 [123].
Fig. 11

Schematization of thermolized at 873 K FeAAm and NiAAm

Among other interesting examples, MCMs based on vinyl derivatives of nitrogen-containing heterocycles (2-vinylpyridine, 4-vinylpyridine, 3,5-dimethyl-1-vinylpyrazole, 2-methyl-5-vinyltetrazole, etc.) should be noted [124, 125]. It is important that the unsaturated ligand has almost no effect on the geometry of the coordination node of the metal, and its double bond retains the ability to undergo addition reactions. Recently, we reviewed the synthesis of chalcogen-containing MCMs and their use as precursors of nanostructured materials [126]. In particular, it is of interest to use of homonuclear tris-dithiocarbamato ruthenium(III) complexes containing allyl or allylmethyl substituents to obtain ruthenium sulfide NPs. Thermolysis of these compounds in hexadecylamine at 493 K makes it possible to obtain Ru2S3 NPs with a cubic crystal structure and a size of 2.5–3.8 nm, capped with hexadecylamine adsorbed on the surfaces of NPs [127]. The thermal decomposition of the Ni(II) and Pt(II) complexes with N-allyl-N′-(4′-methylthiazol)-2ylthiourea proceeds in two stages with the formation of a free metal; a similar Pd(II) complex gives PdS as a residue, while two six-coordinate Co(III) and Cu(II) complexes decompose in three stages with the formation of Co and Cu residues [128]. The TG curves of the Ni(II), Pd(II) and Pt(II) complexes with N-allyl-N′-pyrimidin-2ylthiourea show that the Ni(II) complexes decompose in three stages with the formation of NiO as a residue, while Pd(II) and Pt(II) complexes decompose in two stages with the formation of MS residues [129]. The kinetic parameters (E, ΔH, ΔS, ΔG) of the decomposition stages correlated with the bonding and structural properties of the complexes.

Thus, the thermolysis of MCMs leads to the formation of core–shell nanostructured materials consisting of metal-containing NPs stabilized by a polymeric matrix with a narrow size distribution.

4 Magnetic Materials

Core–shell nanostructured materials obtained by conjugated thermolysis of MCMs have interesting magnetic properties [130, 131]. In particular, the products of thermolysis of unsaturated metal carboxylates, with the exception of CuAcr2, are ferromagnetic (Table 5) [103, 132, 133, 134].
Table 5

The magnetic properties of some unsaturated metal carboxylates and their thermolysis products

MCM

M %

χσ × 105, Gs cm3 g−1

Found/Calc.

σs, Gs cm3 g−1

HC, Oe

jr

Found

292 K

77 K

292 K

77 K

292 K

77 K

292 K

77 K

FeAcr3

24.6

1.75/5.50

3.22/21.0

0.152

0.306

Product of FeAcr3

72.4a

26.1

26.1

33.45

35.94

22.0

233.0

0.051

0.25

NiAcr2

26.1

2.55/2.83

2.55/2.83

0.209

Product of NiAcr2

43.0b

16.7

12.3

14.36

14.95

8.95

53.6

0.02

0.133

CoAcr2

27.5

4.83/2.93

15.1/11.15

0.442

1.41

FeCoAcr

15.4(Fe)

13.7(Co)

2.73/3.17c

6.50/8.63c

0.258

0.742

Product of FeCoAcr

 

41.2

31.1

26.16

13.91

625.0

625.0

0.31

0.42

χσ, magnetic susceptibility; σs, specific magnetization; HC, is coercive force; jr, coefficient of rectangularity

aFor Fe2O3: according to electron diffraction and XRD analysis data, Fe3O4 is the main solid product of thermolysis of FeAcr3

bFor NiO: according to the XRD analysis data, NiO is the main solid product of thermolysis of NiAcr2

cCalculated from experimental data, χσ for FeAcr3 and NiAcr2

The magnetization curves of the thermolysis product of FeAcr3 show that the hysteresis loops are symmetrical with respect to the origin of coordinates and closed [103]. As the temperature increases from 5 to 300 K, the saturation magnetization (MS) changes from 25.66 to 21.82 emu g−1, which is probably due to the antiferromagnetic spin structure of surface atoms. For comparison, the corresponding values for the “bulk” magnetite obtained in the same fields are 98 and 92 emu g−1. The shape of the magnetization curves as a function of temperature, measured in field cooling (FC) and zero-field cooling (ZFC) modes in a field of 0.005 T, shows strong interparticle interactions.

The hysteresis loop for the thermolysis product of CoAcr2 expands with decreasing temperature, and the magnetization of the high field increases [99]. The hysteresis loop at 300 K corresponds to the typical behavior of the material with the preferred ferromagnetic order. The character of the magnetization curve changes substantially at low temperatures, and the susceptibility in high fields increases by almost 5 times, which indicates a significant contribution of the antiferromagnetic CoO phase. In cobalt NPs with a core–shell (Co–CoO) structure, the so-called exchange anisotropy phenomenon is observed, which is associated with the exchange interaction at the interface between two different ferro- and antiferromagnetically ordered systems.

Interesting results were obtained when studying the dependence of the magnetic characteristics of the thermolysis products of NiAcr2 on the thermolysis time [102, 103, 134]. During thermolysis, the magnetization σs and the specific magnetic susceptibility χσ of the original NiAcr2 change (Table 6). The observed nonmonotonic dependence of σs and σF on the thermolysis time is probably associated with a sharp increase in the rate of formation of the ferromagnetic phase at the end of thermolysis. At the last stages of thermolysis, only ~ 25% of Ni atoms are present in the ferromagnetic phase, while other Ni atoms are in the weakly magnetic phase.
Table 6

Variations of the magnetic characteristics of the solid phase during the thermolysis of Ni(Acr)2 at Texp = 643 K

Δm/m0 (wt%)

σs, Gs cm3 g−1

σF, Gs cm3 g−1

χσ × 105, Gs cm3 g−1

ηF

300 K

77 K

300 K

77 K

300 K

77 K

300 K

77 K

0

0.209

0

2.55

0

0

19.1

0.235

0.675

0.024

0.041

2.19

6.70

4.4 × 10−4

7.5 × 10−4

27.1

0.323

1.447

0.084

0.155

2.53

11.8

1.54 × 10−3

2.84 × 10−3

35.4

2.177

1.240

9.9

2.28 × 10−2

46.0

0.93

2.184

0.624

1.949

3.24

11.6

1.14 × 10−2

1.74 × 10−2

51.2

14.36

14.95

12.8

13.78

16.7

12.3

2.35 × 10−1

2.5 × 10−1

Measurements were carried out at a magnetic field strength of 9446 Oe; ηF = σFs(Ni) is the weight fraction of metallic Ni in the sample under the assumption that all ferromagnetism is associated with this phase, and σs(Ni) = 54.5 Gs cm3 g−1

The products of the thermolysis of unsaturated metal dicarboxylates exhibited ferromagnetic behavior at room temperature (Table 7), and hysteresis loops are characteristic of systems with anisotropic exchange [108]. The largest HC (756 Oe) is observed for the nanostructured material obtained by thermolysis of cobalt hydrogen maleate.
Table 7

Magnetic characteristics of nanocomposites obtained by thermolysis of metal dicarboxylates

Precursor

NP diameter (nm)

MS

Mr

Hc, Oe

emu g−1

Acid cobalt itaconate

3.47

0.52

0.062

451

Cobalt hydrogen glutaconate

3.65

15.1

4.67

593

Cobalt hydrogen maleate

4.06

8.4

2.64

756

Cobalt hydrogen allylmalonate

4.08

8.0

1.8

230

Cobalt hydrogen cis,cis-muconate

4.26

2.75

0.53

213

Cobalt acetylenedicarboxylate

9.05

0.63

0.095

510

The bending of the thermomagnetic curve of the FeADC-based nanostructured material (Fig. 12) is due to the presence of a superparamagnetic phase [133].
Fig. 12

Plots of magnetization M versus the magnetic field F for cobalt (a) and iron nanocomposites (b) at different temperatures [133]

In contrast to the products of thermolysis of MCMs of the carboxylate type, the hysteresis loop of the products of thermolysis of CoAAm indicate their ferromagnetic behavior [135]. However, the pattern of the curves shows the probable presence of a disordered interfacial layer with a distorted spin structure on the surface of the magnetic particles. The highest value of Hc is observed for the thermolysis product at 1073 K with a crystallite size of 10–18 nm. With increasing particle size, the effective anisotropy of nanocrystals increases, which leads to a decrease in the role of thermal fluctuations. At the same time, for the thermolysis product of the AAm complex of iron(III) nitrate at 873 K, the shape and pattern of the curves of the hysteresis loop correspond to the ferromagnetic material. The hysteresis loop at 300 K has a slight infiltration, showing the presence of two phases (Fe3C and α-Fe) with different coercive forces (Table 8).
Table 8

Mossbauer spectroscopy data for the AAm complex of Fe(III) nitrate and the products of polymerization and thermolysis at 873 K

Sample

IS

QS

Hhf (T)

Phase composition

Content (wt%)

(mm s−1)

Monomer

0.270

0.650

0.0

PPI

85.70

0.340

1.413

0.0

PPII

14.30

Polymer

0.270

0.650

0.0

PPI

66.63

0.340

1.413

0.0

PPII

33.37

Thermolysis product

0.070

0.000

20.7

Fe3C

86.87

0.073

0.000

32.8

α-Fe

3.170

 

0.840

0.0

PPI, PPII

Residue

IS isomer shift, QS quadrupole splitting, Hhf hyperfine field, PPI and PPII paramagnetic phase

The hysteresis loops for the thermolysis products of NiAAm at 673 and 773 K are characteristic of superparamagnetic particles, while thermolysis at 873 K leads to a ferromagnetic product. A sharp increase in Hc for the thermolysis product at 873 K shows that at this temperature the material switches from a superparamagnet to a ferromagnet. Thus, a change in thermolysis conditions allows one to control the magnetic properties of nanostructured materials from ferromagnetic to superparamagnetic behavior.

Based on the experimental data, multiple regression equations were obtained, linking the properties of nanostructured materials synthesized by the thermolysis of unsaturated nickel dicarboxylates with their magnetic characteristics [136]. It is important that using these equations one can predict the magnetic properties of nanocomposites based on their phase composition, metal content and average diameter of metal-containing NPs. Experimental-statistical mathematical models are also built for nickel itaconate thermolysis to determine the synthetic parameters that would provide the preparation of nanocomposites with tailored characteristics, in particular, with the highest content of the magnetoactive β-nickel phase [137].

5 Sensors

Recently, metal–polymer nanocomposites have become new materials for high-performance gas sensors with low operating temperature and low manufacturing costs [138, 139, 140, 141, 142, 143, 144, 145, 146]. Since gas sensing is a surface phenomenon, the structure and morphology of the surface of such nanomaterials play an important role [102, 147]. When the particle size becomes comparable to the Debye length, the sensor response increases and the response time decreases with decreasing particle size, since the high active surface area promotes rapid adsorption–desorption of gas molecules. In this regard, the “surface accessibility” is crucial for maintaining the high sensitivity of the fabricated sensors [148, 149].

As an example, we consider the sensors of liquefied petroleum gas (LPG), which is the most harmful gas because of its inflammable and explosive nature. To date, various types of LPG sensors have been developed that are of interest for basic research and industrial applications [150, 151, 152, 153, 154, 155].

A highly efficient LPG sensor operating at room temperature with a maximum sensitivity of 23.6 MΩ/s was obtained by thermolysis of the AAm complex of cobalt(II) nitrate [153]. Gas-sensing measurements of these nanocomposites were carried out in a specially designed chamber with openings for gas inlet and outlet (Fig. 13) [155]. In addition, the sensor reproducibility is 96% after one month of observations, which indicates its stability and reliability.
Fig. 13

Chamber diagram for gas-sensing measurements: (1) gas inlet, (2) gas outlet, (3) to a measurement system, (4) disks, (5) pinholes in the disk, (6) silver electrode, (7) glass tube, (8) insulating cylinder, (9) supporting rod, (10) disk spring [148]

Another interesting sensor was obtained by thermolysis of cobalt(II) acetylenedicarboxylate [154]. The maximum sensor response, small response time (Fig. 14) and long-term stability show the promise of the manufactured sensor for detecting LPG.
Fig. 14

Variations of resistance with time (a) and sensor response curves (b) of the LPG sensor [154]

A new approach to the production of metal-sulfide nanocomposite gas-sensitive materials by the thermolysis of Co(II), Cd(II), Zn(II) and Pb(II) acrylamide complexes in the presence of thiourea is proposed [155]. The results of gas sensing show that the morphology of their surface has a significant impact on the efficiency of sensing [156]. Better sensitivity and sensor response, small response and recovery times, as well as long-term stability promise to PbS nanocomposite as the best LPG sensor compared to ZnS nanocomposite (Fig. 15). The maximum sensitivity value was 1.3 GΩ/min for a CdS nanocomposite for 5 vol% of LPG [157]. The detection characteristics of liquefied petroleum gas using nanostructured materials was found to be better or comparable with other LPG sensors [158, 159, 160, 161].
Fig. 15

Variations in sensor response vs. concentration of LPG [157]

Another interesting direction is the use a nanostructured material obtained by thermolysis of the AAm complex of nickel(II) nitrate as a humidity sensor [98]. Nanocomposite was used for two different modes of humidity sensing: impedance-based electrical humidity measurement and transmission-based opto-electronic humidity measurement (Fig. 16). The values of the maximum average sensitivity of 37.79 MΩ/%RH and 1.31 µW/%RH, respectively, were obtained at room temperature.
Fig. 16

Variation of output power with %RH for humidity sensor a sensing response, b repeatability, c ageing effect after three and four weeks and d response and recovery times [98]

A nanostructured material obtained by thermolysis of the AAm complex of zinc(II) nitrate was used as a transmission-based optoelectronic humidity sensor [162]. The maximum sensitivity was determined to be 1.831 µW/%RH, and the response and recovery times of the sensor were 250 and 37 s, respectively. In addition, it turned out that the sensor was ~ 96% stable after a long run.

6 Catalysts

In recent years, metal-containing nanomaterials have been intensively studied as catalysts because of their unique physicochemical properties [61, 123], the high ratio of surface atoms to the total number of atoms in a particle, and the ability to vary the catalytic properties, controlling particle size [163, 164, 165, 166, 167, 168, 169, 170]. As a typical example, the zero-valent complexes of palladium and NPs, which are well-known as effective and selective catalysts for many organic reactions, should be noted [171, 172, 173, 174, 175]. Aggregation and agglomeration of NPs limit their use as catalysts; therefore, they are fixed on carriers (metal oxides, zeolites, carbon, etc.) or stabilized by various types of ligands, including polymers.

Among the new approaches to the synthesis of immobilized mixed catalysts, we note the thermolysis of MCMs (AAm complexes of transition metals) in the presence of a highly dispersed inorganic carrier [176]. As a result of thermolysis, a polymer-inorganic composite is formed with inclusions of Pd NPs stabilized by a polymer matrix on the surface of the carrier. It turned out that these nanocomposites are effective catalysts for the reduction of nitro compounds [176], the hydrogenation of cyclohexene, alkene and acetylene alcohols, as well as di- and trinitrotoluene [177]. The nature of the inorganic carrier has a significant effect on the activity and selectivity in the hydrogenation of allyl alcohol (Table 9). A higher reaction rate when using SiO2 is apparently due to a more developed surface area of the catalyst and the specific adsorption of the substrate molecule on the surface of the catalysts.
Table 9

Initial rates and selectivity of the hydrogenation of allyl alcohol and 3,7,11,15-tetramethylhexadec-1-yn-3-ol on Pd hybrid polymer-immobilized catalysts

Carrier

Allyl alcohol

C20 acetylene alcohol

w × 105, mol L−1 s−1

Selectivity (%)

w × 105, mol L−1 s−1

(after 10 min)

Selectivity (%)

Al2O3

4.98

97.2

1.4

70

SiO2

56.7

95.6

2.8

49.9

Reaction conditions: alcohol concentration: 0.225 mol/L; catalyst sample weight: 0.03 g (1.41 × 10−5 g at of Pd/g); temperature: 40 °C; pressure: 0.1 MPa; solvent: 20 mL of ethanol

Similar rhodium-containing hybrid nanocomposites were tested as catalysts for the hydrogenation of various unsaturated compounds (cyclohexene, olefinic and acetylenic alcohols) and the selective reduction of di- and trinitrotoluene [178]. In this case, the activity of the supported catalyst obtained by thermolysis (Fig. 17) is almost two times higher than that of the standard Rh/C catalyst.
Fig. 17

Kinetics of hydrogen uptake in the hydrogenation of cyclohexene in the presence of Rh-containing nanocomposites based on inorganic carriers: (1) SiO2, (2) C, (3) Al2O3, and (4) Rh/C. The catalyst weight was 0.10–0.102 g, the temperature was 40 °C, the H2 pressure was 0.1 MPa, the solvent was isopropanol, and the amount of cyclohexene was 6.9 mmol [178]

7 Tribological Materials

One of the promising areas for the use of metal-containing nanomaterials is the development of highly effective additives to engine oils (nanolubricants), which can significantly reduce engine wear and friction [179]. Nanolubricants are used to overcome the drawbacks of conventional anti-wear and anti-friction additives that require chemical reactions with substrates and, therefore, an induction period to obtain a tribo-film on the friction surface [180, 181, 182, 183, 184, 185, 186, 187, 188, 189, 190, 191]. Functionalization of the surface of the NPs allows you to adjust the colloidal stability of the dispersion of the NPs and increase their lubricity. It is important that functionalized NPs have a hybrid structure with a rigid inner core and a soft outer shell, which provides a higher load carrying capacity without reducing lubricity [192].

Core–shell nanomaterials obtained by conjugated thermolysis of MCMs were shown to be effective additives to liquid paraffin. In particular, the addition of Co3O4 NPs obtained by thermolysis of cobalt acrylate complexes with bpy and phen to liquid paraffin reduces the coefficient of friction (COF) at a rather low concentration of 0.05% in 0.6 times (Fig. 18) [86]. This concentration is optimal for obtaining a minimum COF value. The optimum load value was found, at which a decrease in COF is observed.
Fig. 18

Dependence of the coefficient of friction on the concentration of the additive [86]

Similar laws were established in the study of nanomaterials obtained by the thermolysis of nickel cinnamate complexes with bpy and phen [113]. In this case, the optimal concentration of the additive is also 0.05 wt%. At the same time, when using the product of thermolysis of nickel maleate complexes with bpy (MCM 1), the highest efficiency is achieved when the concentration of the additive obtained by thermolysis of MCM 1 in the lubricant is 0.8 wt % [193]. The addition of NiO NPs obtained by thermolysis of nickel maleate complexes with phen (MCM 2) as additives to liquid paraffin reduces COF at a fairly low concentration of 0.5%. Thus, the optimum concentration is highly dependent on the system, since the composition of the lubricant must be adjusted for each operating condition. Figure 19 shows a plot of COF versus load at a constant additive concentration of 0.05%. For nanolubricant based on the product of thermolysis of MCM 1 with increasing load from 49 to 98 N COF first increases, then remains unchanged to 147 N. With a further increase in load to 245 N, a decrease in COF is observed. At the same time, for a nanolubricant based on the thermolysis product of MCM 2, COF decreases with increasing load.
Fig. 19

The effect of load on COF at a constant concentration of the additive of 0.05%: left—the product of thermolysis of MCM 1, right—the product of thermolysis of MCM 2 [193]

The introduction of metal-containing nanomaterials into a lubricant improves its anti-wear properties and is explained by the formation of a metal film in the contact zone of rubbing surfaces (tribo-film). The formation of a film prevents direct contact of the metal with the metal and determines the tribological behavior of interacting surfaces [181]. Tribo-film formation is initiated by the reaction between rubbing material and additives under ambient conditions [194, 195, 196, 197, 198].

8 Concluding Remarks and Outlook

Thus, the study of the production of core–shell nanostructured nanomaterials by thermolysis of MCMs indicates the integration of the synthesis of NPs with their simultaneous stabilization in a decarboxylated matrix of controlled thickness (the “one-pot” process). The current stage of research in this area has reached its peak in the accumulation of experimental facts, their theoretical interpretation and generalization.

How do we see the development of this interesting and promising area of research for metal-containing nanomaterials?

Firstly, of interest is the directed synthesis of new types of MCMs and the modification of known MCMs. Recently, we reviewed design strategies for MCMs [63]. As an example, we note the synthesis of MCMs based on mixed ligands, including unsaturated carboxylic acid and various nitrogen-containing ligands (derivatives of bpy, phen, terpyridine, etc.). Another promising direction is to obtain MCMs, in which donor sites include non-traditional heteroatoms, for example, Se or Te. Optimization of methods for the synthesis of MCMs will be continued by reducing the number of stages of synthesis (for example, by combining the synthesis of unsaturated ligand and MCM based on it, etc.).

Secondly, the synthesis and study of the conjugated thermolysis of polymetallic MCMs should be noted. Thus, ferrites were obtained by thermolysis of hydrazined mixed metal fumarates [199, 200, 201], trimetallic fumarate [202], and others.

Thirdly, it is of interest to use a mixture of some MCMs in the process of thermolysis. Thus, Co and Mn fumarates were used as precursors for the target synthesis of cobalt-based catalysts for alcohol reforming [203]. It turned out that this catalyst consists mainly of metallic cobalt and MnO dispersed in the carbon matrix.

In addition, it is of considerable interest to solve the following important tasks:
  • determination of the kinetic regularities of thermolysis processes with the participation of MCMs;

  • study of changes in the metal ion and the unsaturated ligand during conjugated thermolysis;

  • determination of the structure of the formed metal-polymer nanostructured materials, the study of their morphology and topochemistry.

Special attention will be paid to the search for new fields of application of core–shell nanostructured materials. In this review, we considered as an example their use as magnetic materials, sensors, catalysts, and tribological materials. Among other interesting examples, we note the use of composites containing magnetic Ni nanocrystallites entrapped in a carbon matrix for the treatment of hyperthermia [134].

However, as a rule, it is still not possible to find correlations between the composition, structural features and properties of core–shell nanostructured materials, which greatly complicates the development of a scientifically based approach to structuring these materials and predicting their promising properties.

Notes

Compliance with Ethical Standards

Conflict of interest

The authors declare no competing financial interest.

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© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Laboratory of MetallopolymersThe Institute of Problems of Chemical Physics RASChernogolovkaRussian Federation
  2. 2.Department of ChemistrySouthern Federal UniversityRostov-on-DonRussian Federation

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